TWI680206B - Activation method for silicon substrates - Google Patents

Activation method for silicon substrates Download PDF

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TWI680206B
TWI680206B TW105108607A TW105108607A TWI680206B TW I680206 B TWI680206 B TW I680206B TW 105108607 A TW105108607 A TW 105108607A TW 105108607 A TW105108607 A TW 105108607A TW I680206 B TWI680206 B TW I680206B
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acid
aromatic
silicon substrate
acids
metal
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TW201641745A (en
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克里斯多夫 蘇誠傳克
Christof Suchentrunk
克利斯汀 許華茲
Christian Schwarz
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德商德國艾托特克公司
Atotech Deutschland Gmbh
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Abstract

本發明係關於一種用於活化矽基材之活化組合物，其係包含鈀離子源、氟離子源及至少兩種芳香族酸之水溶液。本發明進一步係關於其使用及視情況用於此等經處理之基材之隨後金屬化之方法。該方法可用於半導體及太陽能電池製造中。 The invention relates to an activating composition for activating a silicon substrate, which comprises an aqueous solution of a palladium ion source, a fluoride ion source, and at least two aromatic acids. The invention further relates to a method for its use and, as appropriate, subsequent metallization of these treated substrates. This method can be used in semiconductor and solar cell manufacturing.

Description

矽基材之活化方法 Method for activating silicon substrate

本發明係關於太陽能電池及電子裝置之製造，具體而言係關於在無電金屬化及矽化物互連之形成之前矽基材之活化方法，該等互連可用於電晶體(MOS、CMOS)、記憶條、MS及SD卡中。 The present invention relates to the manufacture of solar cells and electronic devices, and specifically relates to a method for activating a silicon substrate before formation of electroless metallization and silicide interconnections. These interconnections can be used in transistors (MOS, CMOS), Memory stick, MS and SD card.

一般而言，矽化物互連係藉由將諸如鎳等金屬無電沈積於適宜矽基材上且隨後熱處理以形成金屬矽化物來形成。此熱處理通常稱為快速熱退火(RTA)。通常，此熱處理需要基材經受300℃至750℃範圍內之升高之溫度，藉此在金屬矽化物形成之後金屬擴散至矽基材中。對於欲沈積於矽基材上之金屬，該等矽基材需要經活化。此情形尤其針對p型摻雜之多晶矽。n型摻雜之基材可直接使用強鹼性無電鎳電鍍浴來電鍍。然而，強鹼性介質可損壞製造半導體中所用之基材，例如焊料遮罩。因此，業內不期望使用強鹼性電鍍浴。因此，使用包含鈀離子及氫氟酸或如GB 976,656中所揭示之其他氟離子源之組合物來活化矽基材係常用技術。此類型之活化之可能機制揭示於US 4,297,393中。 Generally, silicide interconnects are formed by electrolessly depositing a metal such as nickel on a suitable silicon substrate and subsequent heat treatment to form a metal silicide. This heat treatment is commonly referred to as rapid thermal annealing (RTA). Generally, this heat treatment requires the substrate to be subjected to an elevated temperature in the range of 300 ° C to 750 ° C, whereby the metal diffuses into the silicon substrate after the metal silicide is formed. For metals to be deposited on silicon substrates, the silicon substrates need to be activated. This situation is especially true for p-doped polycrystalline silicon. The n-type doped substrate can be directly plated using a strong alkaline electroless nickel plating bath. However, strongly alkaline media can damage substrates used in the manufacture of semiconductors, such as solder masks. Therefore, it is not desirable in the industry to use a strong alkaline plating bath. Therefore, the use of a composition containing palladium ions and hydrofluoric acid or other fluoride ion sources as disclosed in GB 976,656 to activate silicon substrates is a common technique. A possible mechanism for this type of activation is disclosed in US 4,297,393.

US 6,406,743 B1係關於多晶矽互連上之矽化鎳形成。其中所揭示之方法教示使用含有鈀鹽及高濃度之氫氟酸及乙酸之溶液作為在鎳或鎳合金沈積之前多晶矽之活化組合物。不管與使用此濃氫氟酸溶液相關之高毒性如何，此組合物之使用導致獲得極粗糙鈀晶種。為了在 此等粗糙鈀晶種上提供均勻矽化鎳覆蓋，需要在其上提供厚鎳沈積物，此進而導致結構太大而不能用於現代半導體技術中(參見實例1及2)。 US 6,406,743 B1 relates to the formation of nickel silicide on polycrystalline silicon interconnects. The method disclosed therein teaches the use of a solution containing a palladium salt and a high concentration of hydrofluoric acid and acetic acid as an activating composition for polycrystalline silicon prior to the deposition of nickel or a nickel alloy. Regardless of the high toxicity associated with the use of this concentrated hydrofluoric acid solution, the use of this composition resulted in the obtaining of extremely rough seed crystals of palladium. In order Providing uniform nickel silicide coverage on these rough palladium seeds requires thick nickel deposits thereon, which in turn results in structures that are too large to be used in modern semiconductor technology (see examples 1 and 2).

US 5,753,304報導了具體而言用於鋁表面之活化溶液。該活化溶液尤其包含鈀鹽、鹼金屬氟化物或氟化氫及作為錯合劑之羧酸。該等羧酸係以約10ml/l活化溶液至100ml/l活化溶液之量使用。 US 5,753,304 reports activating solutions specifically for aluminum surfaces. The activation solution contains, in particular, a palladium salt, an alkali metal fluoride or hydrogen fluoride, and a carboxylic acid as a complexing agent. These carboxylic acids are used in an amount of about 10 ml / l of activation solution to 100 ml / l of activation solution.

US 2005/0161338 A1揭示使用包含鈀源及至少一種酸之水溶液來活化矽表面之方法。本揭示內容中可用之酸有多種，例如礦酸，如硫酸、硝酸及鹽酸；或有機硫酸，例如甲烷硫酸；或芳香族磺酸，例如對甲苯磺酸。然而，使用一種脂肪族或芳香族酸導致所處理表面之覆蓋極不均勻(參見實例2至4)。 US 2005/0161338 A1 discloses a method for activating a silicon surface using an aqueous solution containing a source of palladium and at least one acid. There are many acids that can be used in this disclosure, such as mineral acids such as sulfuric acid, nitric acid, and hydrochloric acid; or organic sulfuric acids, such as methane sulfuric acid; or aromatic sulfonic acids, such as p-toluenesulfonic acid. However, the use of an aliphatic or aromatic acid results in extremely uneven coverage of the treated surface (see Examples 2 to 4).

WO 2014/128420揭示包含陰離子或非離子表面活性劑、金離子及氟離子之組合物用於活化半導體基材之用途。表面活性劑之採用改良了結果且使得形成較薄鎳層。根據此揭示內容，含有鈀及氟離子之組合物導致不均勻沈積且隨後鎳層擴散於基材上及基材中(第2、14及15頁及表1，條目1)。由於若干原因(例如成本)，在電子裝置之製造中使用金離子係不期望的。 WO 2014/128420 discloses the use of a composition comprising an anionic or non-ionic surfactant, gold ions and fluoride ions for activating a semiconductor substrate. The use of a surfactant improves the results and results in a thinner nickel layer. According to this disclosure, a composition containing palladium and fluoride ions results in uneven deposition and subsequent diffusion of a nickel layer on and into the substrate (pages 2, 14, and 15 and Table 1, entry 1). The use of gold ion systems in the manufacture of electronic devices is not desirable for several reasons, such as cost.

儘管該等方法能夠提供用於活化矽基材及隨後矽化鎳形成之方法，但其不能滿足現代半導體製造之需要。所採用之貴金屬之晶種層太粗糙且個別晶種於矽基材表面上之分佈不夠均勻，且導致必須於基材上沈積極厚的鎳層。此外，若貴金屬分佈太粗糙，則個別貴金屬粒子亦較大，從而因貴金屬之價格通常較高而導致成本增加。甚至更重要地，矽基材上之金屬或金屬層需要極薄且具有均勻高度。因此，其需要平坦並光滑。因此，前提條件係下伏鈀晶種層極均勻且實質上不含較大聚集粒子。若鈀晶種與欲於其上形成之期望之金屬或金屬合金層一樣大(或甚至更大)，則此尤其不利。於其上形成之金屬或金屬合 金層將另外於彼等大粒子上形成且將形成需要拋光步驟之極粗糙(產生如山谷及丘陵之結構)表面，尤其在欲形成在5nm、10nm、20nm或50nm範圍內之金屬或金屬合金層之情形下。此與半導體製造工業中之持續小型化以及成本及環境意識不相容。 Although these methods can provide methods for activating a silicon substrate and subsequent formation of nickel silicide, they cannot meet the needs of modern semiconductor manufacturing. The seed layer of the precious metal used is too rough and the individual seeds are not evenly distributed on the surface of the silicon substrate, resulting in the necessity to deposit a very thick nickel layer on the substrate. In addition, if the noble metal distribution is too rough, individual noble metal particles are also large, resulting in an increase in cost due to the usually high price of the noble metal. Even more importantly, the metal or metal layer on the silicon substrate needs to be extremely thin and of uniform height. Therefore, it needs to be flat and smooth. Therefore, the prerequisite is that the underlying palladium seed layer is extremely uniform and does not substantially contain large aggregated particles. This is particularly disadvantageous if the palladium seed is as large (or even larger) than the desired metal or metal alloy layer to be formed thereon. Metal or metal alloy formed thereon Gold layers will additionally be formed on their large particles and will form extremely rough (producing structures such as valleys and hills) surfaces that require polishing steps, especially for metals or metal alloys that are to be formed in the 5nm, 10nm, 20nm, or 50nm range Case. This is incompatible with continued miniaturization and cost and environmental awareness in the semiconductor manufacturing industry.

本發明之目標 Object of the invention

因此，本發明之目標係克服如上文所提及之缺點以提供活化組合物及其使用方法，該方法尤其使得於矽基材上形成具有優良表面覆蓋之極薄鈀晶種層。 Therefore, the object of the present invention is to overcome the disadvantages mentioned above to provide an activating composition and a method of using the same, which in particular makes it possible to form an extremely thin palladium seed layer with excellent surface coverage on a silicon substrate.

因此，本發明之另一目標係提供上面均勻覆蓋有鈀晶種層之矽基材，其可用於無電金屬化。 Therefore, another object of the present invention is to provide a silicon substrate uniformly covered with a palladium seed layer, which can be used for electroless metallization.

本發明之另一目標係提供金屬矽化物互連形成、具體而言矽化鎳互連形成之方法，其符合如今半導體工業中之小型化要求。 Another object of the present invention is to provide a method for forming a metal silicide interconnect, specifically a nickel silicide interconnect, which meets the miniaturization requirements in the semiconductor industry today.

該等目標係藉由使用本發明活化組合物而解決。本發明之用於活化矽基材之活化組合物係包含鈀離子源及氟離子源之水溶液，其特徵在於其包含至少兩種(彼此獨立)選自由以下組成之群之芳香族酸：芳香族羧酸、芳香族磺酸、芳香族亞磺酸、芳香族膦酸及芳香族次膦酸。 These objectives are solved by using the activating composition of the present invention. The activating composition for activating a silicon substrate of the present invention comprises an aqueous solution of a palladium ion source and a fluoride ion source, which is characterized in that it contains at least two (independent of each other) aromatic acids selected from the group consisting of: aromatic Carboxylic acid, aromatic sulfonic acid, aromatic sulfinic acid, aromatic phosphonic acid and aromatic phosphinic acid.

該等目標進一步藉由用於活化至少一種矽基材之本發明方法而解決，該方法以給定順序包含以下步驟：(i)提供至少一種矽基材；(ii)使用包含以下之水溶液作為活化組合物來活化該至少一種矽基材之表面之至少一部分：鈀離子源、氟離子源及至少兩種至少兩種(彼此獨立)選自由以下組成之群之芳香族酸：芳香族羧酸、芳香族磺酸、芳香族亞磺酸、芳香族膦酸及芳香族次膦酸。 These objectives are further solved by the method of the present invention for activating at least one silicon substrate, which method comprises the following steps in a given order: (i) providing at least one silicon substrate; (ii) using an aqueous solution containing the following An activating composition to activate at least a portion of the surface of the at least one silicon substrate: a palladium ion source, a fluoride ion source, and at least two (independent of each other) aromatic acids selected from the group consisting of: , Aromatic sulfonic acid, aromatic sulfinic acid, aromatic phosphonic acid and aromatic phosphinic acid.

圖1係使用由氫氟酸及鈀離子組成之比較水性活化組合物處理之n型摻雜之矽基材之SEM圖片(對應實例1)。 Figure 1 is a SEM picture of a n-type doped silicon substrate treated with a comparative aqueous activating composition consisting of hydrofluoric acid and palladium ions (corresponding to Example 1).

圖2係使用由氫氟酸、乙酸及鈀離子組成之比較水性活化組合物處理之n型摻雜之矽基材之SEM圖片(對應實例2)。 FIG. 2 is an SEM picture of a n-type doped silicon substrate treated with a comparative aqueous activating composition consisting of hydrofluoric acid, acetic acid, and palladium ions (corresponding to Example 2).

圖3至7係使用含有氫氟酸、鈀離子及一或多種芳香族酸之本發明水性活化組合物處理之多晶矽基材之SEM圖片。圖3至7與實例4a至4e相關。 3 to 7 are SEM pictures of a polycrystalline silicon substrate treated with an aqueous activating composition of the present invention containing hydrofluoric acid, palladium ions, and one or more aromatic acids. Figures 3 to 7 relate to examples 4a to 4e.

圖8係使用本發明活化溶液處理、隨後使用無電鎳電鍍浴處理之n型摻雜之多晶矽基材之AFM圖片(與實例5a相關)。 FIG. 8 is an AFM picture of an n-doped polycrystalline silicon substrate treated with an activation solution of the present invention and subsequently treated with an electroless nickel plating bath (relative to Example 5a).

本發明之用於活化矽基材之活化組合物係包含鈀離子源、氟離子源及至少兩種選自由以下組成之群之芳香族酸之水溶液：芳香族羧酸、芳香族磺酸、芳香族亞磺酸、芳香族膦酸及芳香族次膦酸。在本發明之較佳實施例中，至少兩種芳香族酸選自由以下組成之群：芳香族羧酸、芳香族磺酸及芳香族膦酸。 The activating composition for activating a silicon substrate of the present invention comprises an palladium ion source, a fluoride ion source, and an aqueous solution of at least two aromatic acids selected from the group consisting of: aromatic carboxylic acid, aromatic sulfonic acid, aromatic Group sulfinic acid, aromatic phosphonic acid and aromatic phosphinic acid. In a preferred embodiment of the present invention, the at least two aromatic acids are selected from the group consisting of aromatic carboxylic acids, aromatic sulfonic acids, and aromatic phosphonic acids.

應理解，在本發明之上下文中芳香族羧酸係包含至少一個羧酸部分(-CO2H)之芳香族化合物。類似地，芳香族磺酸係包含至少一個磺酸部分(-SO3H)之芳香族化合物。芳香族亞磺酸係包含至少一個亞磺酸部分(-SO2H)之芳香族化合物，芳香族膦酸係包含至少一個膦酸部分(-PO3H2)之芳香族化合物且芳香族次膦酸係包含至少一個次膦酸部分(-PO2H2)之芳香族化合物。 It should be understood, in the context of the present invention comprises an aromatic carboxylic aromatic compound having at least one carboxylic acid moiety (-CO 2 H) of the. Similarly, the aromatic sulfonic acid is an aromatic compound containing at least one sulfonic acid moiety (—SO 3 H). Aromatic sulfinic acid is an aromatic compound containing at least one sulfinic acid moiety (-SO 2 H), and aromatic phosphonic acid is an aromatic compound including at least one phosphonic acid moiety (-PO 3 H 2 ) and is aromatic. A phosphonic acid is an aromatic compound containing at least one phosphinic acid moiety (-PO 2 H 2 ).

芳香族化合物進一步包含至少一個環狀烴基，例如苯基或萘基，其中個別環碳原子可由N、O及/或S替代，例如苯并噻唑基或吡啶基(例如通常稱為菸鹼酸之3-吡啶甲酸中)。此外，鍵結至芳香族化合物之個別氫原子可在每一情形下藉由官能基取代，該官能基係例如胺基、羥基、硝基、烷基、芳基、鹵化物(例如氟化物、氯化物、溴 化物、碘化物)、羰基、衍生自上文所提及之酸部分中任一者之酯等。芳香族化合物亦可包含至少一個由兩個或更多個縮合環組成之烴基(如菲或蒽)，只要足夠官能基附接至其以保證足夠高濃度之水溶解性即可。術語「羥基(hydroxy及hydroxyl)」作為有機部分在本文中可互換使用。業內有時將部分稱為殘基或基團。 Aromatic compounds further include at least one cyclic hydrocarbon group, such as phenyl or naphthyl, in which individual ring carbon atoms can be replaced by N, O, and / or S, such as benzothiazolyl or pyridyl (such as 3-picolinic acid). In addition, individual hydrogen atoms bonded to an aromatic compound may be substituted in each case by a functional group such as an amine, hydroxyl, nitro, alkyl, aryl, halide (e.g. fluoride, Chloride, bromine Compounds, iodides), carbonyls, esters derived from any of the acid moieties mentioned above, and the like. The aromatic compound may also include at least one hydrocarbon group (such as phenanthrene or anthracene) composed of two or more condensed rings, as long as sufficient functional groups are attached thereto to ensure a sufficiently high concentration of water solubility. The terms "hydroxy and hydroxyl" are used interchangeably herein as the organic moiety. The industry sometimes refers to portions as residues or groups.

就用於此說明書及申請專利範圍中之術語「烷基」而言，其係指具有化學通式CmH2m+1之烴基，m係自1至約50之整數。本發明烷基部分可係直鏈及/或具支鏈的且其可係飽和及/或不飽和的。若烷基部分不飽和，則對應的化學通式必須相應調整。較佳地，m在1至12、更佳1至8、甚至更佳1至4範圍內。C1-C8-烷基尤其包括(例如)甲基、乙基、正丙基、異丙基、正丁基、異丁基、第三丁基、正戊基、異戊基、第二戊基、第三戊基、新戊基、己基、庚基及辛基。此一烷基之一或多個氫原子亦可藉由以下官能基取代：例如胺基、羥基、硫醇、鹵化物(例如氟化物、氯化物、溴化物、碘化物)、羰基、羧基、羧酸酯、膦酸酯等。 As used in this specification and the scope of patent applications, the term "alkyl" refers to a hydrocarbon group having the general formula C m H 2m + 1 , and m is an integer from 1 to about 50. The alkyl moiety of the present invention may be linear and / or branched and it may be saturated and / or unsaturated. If the alkyl moiety is unsaturated, the corresponding chemical formula must be adjusted accordingly. Preferably, m is in the range of 1 to 12, more preferably 1 to 8, and even more preferably 1 to 4. C 1 -C 8 -alkyl includes, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, third butyl, n-pentyl, isopentyl, second Amyl, tertiary, neopentyl, hexyl, heptyl, and octyl. One or more hydrogen atoms of this alkyl group may also be substituted by the following functional groups: for example, amine, hydroxyl, thiol, halide (such as fluoride, chloride, bromide, iodide), carbonyl, carboxyl, Carboxylate, phosphonate, etc.

較佳地，酸部分中之至少一者經由碳-碳、碳-硫或碳-磷單鍵直接鍵結至芳香族化合物之芳基。更佳地，所有酸部分直接鍵結至芳基。 Preferably, at least one of the acid moieties is directly bonded to the aromatic group of the aromatic compound via a carbon-carbon, carbon-sulfur or carbon-phosphorus single bond. More preferably, all acid moieties are directly bonded to the aryl group.

在本發明之較佳實施例中，至少兩種芳香族酸選自如式(I)至(II)之芳香族酸

Figure TWI680206B_D0001
及
Figure TWI680206B_D0002
 In a preferred embodiment of the present invention, at least two aromatic acids are selected from aromatic acids such as formulae (I) to (II)
Figure TWI680206B_D0001
and
Figure TWI680206B_D0002

其中R1至R14彼此獨立選自由以下組成之群：氫(-H)、烷基、芳基、諸如氯化物(-Cl)等鹵化物、胺基(-NH2)、羧酸部分(-CO2H)、磺酸部分(-SO3H)、亞磺酸部分(-SO2H)、膦酸部分(-PO3H2)、次膦酸部分(-PO2H2)、硝基(-NO2)及羥基(-OH)，前提係R1至R14中之至少一者係羧酸部分(-CO2H)、磺酸部分(-SO3H)、亞磺酸部分(-SO2H)、膦酸部分(-PO3H2)或次膦酸部分(-PO2H2)、較佳磺酸部分、羧酸部分或膦酸部分。羧酸部分(-CO2H)、磺酸部分(-SO3H)、亞磺酸部分(-SO2H)、膦酸部分(-PO3H2)及次膦酸部分(-PO2H2)在本文中統稱為「酸部分」。 Wherein R 1 to R 14 are independently selected from the group consisting of hydrogen (-H), alkyl, aryl, halide such as chloride (-Cl), amine (-NH 2 ), carboxylic acid moiety ( -CO 2 H), sulfonic acid part (-SO 3 H), sulfinic acid part (-SO 2 H), phosphonic acid part (-PO 3 H 2 ), phosphinic acid part (-PO 2 H 2 ), Nitro (-NO 2 ) and hydroxyl (-OH), provided that at least one of R 1 to R 14 is a carboxylic acid moiety (-CO 2 H), a sulfonic acid moiety (-SO 3 H), or a sulfinic acid Part (-SO 2 H), phosphonic acid part (-PO 3 H 2 ) or phosphinic acid part (-PO 2 H 2 ), preferably sulfonic acid part, carboxylic acid part or phosphonic acid part. Carboxylic acid part (-CO 2 H), sulfonic acid part (-SO 3 H), sulfinic acid part (-SO 2 H), phosphonic acid part (-PO 3 H 2 ), and phosphinic acid part (-PO 2 H 2 ) is collectively referred to herein as the "acid moiety".

較佳地，僅一種類型之酸部分包含於單一芳香族酸中。此意味著(例如)若芳香族酸包含一或多個羧酸部分，則其較佳不含如磺酸、亞磺酸、膦酸及次膦酸部分等其他酸部分。 Preferably, only one type of acid moiety is contained in a single aromatic acid. This means that, for example, if the aromatic acid contains one or more carboxylic acid moieties, it is preferably free of other acid moieties such as sulfonic acid, sulfinic acid, phosphonic acid, and phosphinic acid moieties.

式(I)至(II)之芳香族酸通常充分溶於水中以用於本發明活化組合物中。若芳香族酸之溶解性不夠，則可採用熟習此項技術者已知之共溶劑及表面活性劑以增加芳香族酸於活化組合物中之溶解性。 The aromatic acids of formulae (I) to (II) are generally sufficiently soluble in water for use in the activating composition of the present invention. If the solubility of the aromatic acid is insufficient, co-solvents and surfactants known to those skilled in the art can be used to increase the solubility of the aromatic acid in the activating composition.

在甚至更佳實施例中，至少兩種式(I)至(II)之芳香族酸包含彼此獨立選自由以下組成之群之R1至R14：氫、烷基、芳基、胺基、磺酸部分、羧酸部分、硝基及羥基，前提係至少兩種芳香族酸中之每一者包含獨立選自由羧酸部分及磺酸部分組成之群之R1至R14中之一者。 In an even more preferred embodiment, the at least two aromatic acids of the formulae (I) to (II) comprise R 1 to R 14 independently of one another selected from the group consisting of: hydrogen, alkyl, aryl, amine, Sulfonic acid moiety, carboxylic acid moiety, nitro group, and hydroxyl group, provided that each of at least two aromatic acids includes one independently selected from the group consisting of R 1 to R 14 consisting of a carboxylic acid moiety and a sulfonic acid moiety .

在本發明之又一甚至更佳實施例中，活化組合物中之至少兩種芳香族酸之至少一種芳香族酸包含磺酸部分。在本發明之第二甚至更佳實施例中，活化組合物包含包括羧酸部分之至少兩種芳香族酸中之至少一種芳香族酸。在本發明之第三甚至更佳實施例中，活化組合物含有至少一種包含磺酸部分之芳香族酸及至少一種包含羧酸部分之芳香族酸。 In yet another even more preferred embodiment of the present invention, at least one aromatic acid of the at least two aromatic acids in the activating composition comprises a sulfonic acid moiety. In a second or even preferred embodiment of the invention, the activating composition comprises at least one aromatic acid of at least two aromatic acids including a carboxylic acid moiety. In a third or even more preferred embodiment of the present invention, the activating composition contains at least one aromatic acid comprising a sulfonic acid moiety and at least one aromatic acid comprising a carboxylic acid moiety.

在如式(I)至(II)之包含至少一個磺酸部分之芳香族磺酸中，較佳 R1至R14中之至少一者係羥基及/或胺基，更佳不為磺酸部分之R1至R14全部均選自氫、胺基及羥基。活化組合物中之此等酸似乎可改良如此處理之矽基材之表面覆蓋。 In the aromatic sulfonic acid containing at least one sulfonic acid moiety as in formulas (I) to (II), preferably at least one of R 1 to R 14 is a hydroxyl group and / or an amine group, and more preferably not a sulfonic acid Part of R 1 to R 14 are all selected from hydrogen, amine and hydroxyl. These acids in the activating composition appear to improve the surface coverage of the silicon substrate thus treated.

在另一甚至更佳實施例中，欲用於本發明活化組合物中之至少兩種芳香族酸選自由以下組成之群：苯甲酸、1,2-苯二甲酸(鄰苯二甲酸)、1,3-苯二甲酸(間苯二甲酸)、1,4-苯二甲酸(對苯二甲酸)、1,2,3-苯三甲酸(半蜜臘酸)、1,2,4-苯三甲酸(偏苯三酸)、1,3,5-苯三甲酸(苯均三酸)、1,2,4,5-苯四甲酸(焦蜜石酸)、1,2,3,4,5-苯五甲酸、1,2,3,4,5,6-苯六甲酸(蜜臘酸)、2-硝基苯甲酸、3-硝基苯甲酸、4-硝基苯甲酸、2,5-二硝基苯甲酸、2,6-二硝基苯甲酸、3,5-二硝基苯甲酸、2，4-二硝基苯甲酸、3,4-二硝基苯甲酸、2-胺基苯甲酸、3-胺基苯甲酸、4-胺基苯甲酸、3,4-二胺基苯甲酸、3,5-二胺基苯甲酸、2,3-胺基苯甲酸、2,4-二胺基苯甲酸、柳酸、對甲苯磺酸、1-萘甲酸、2-萘甲酸、2,6-萘二甲酸、2-萘磺酸、5-胺基-1-萘磺酸、5-胺基-2-萘磺酸、7-胺基-4-羥基-2-萘磺酸及苯基膦酸。 In another even better embodiment, the at least two aromatic acids to be used in the activating composition of the present invention are selected from the group consisting of benzoic acid, 1,2-phthalic acid (phthalic acid), 1,3-phthalic acid (isophthalic acid), 1,4-phthalic acid (terephthalic acid), 1,2,3-benzenetricarboxylic acid (hemamic acid), 1,2,4- Trimellitic acid (trimellitic acid), trimellitic acid (trimesic acid), trimellitic acid (pyromelic acid), 1, 2, 3, 4,5-benzenepentacarboxylic acid, 1,2,3,4,5,6-melanic acid (melanic acid), 2-nitrobenzoic acid, 3-nitrobenzoic acid, 4-nitrobenzoic acid, 2,5-dinitrobenzoic acid, 2,6-dinitrobenzoic acid, 3,5-dinitrobenzoic acid, 2,4-dinitrobenzoic acid, 3,4-dinitrobenzoic acid, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 3,4-diaminobenzoic acid, 3,5-diaminobenzoic acid, 2,3-aminobenzoic acid, 2,4-diaminobenzoic acid, salicylic acid, p-toluenesulfonic acid, 1-naphthoic acid, 2-naphthoic acid, 2,6-naphthalenedicarboxylic acid, 2-naphthalenesulfonic acid, 5-amino-1-naphthalene Sulfonic acid, 5-amino-2-naphthalenesulfonic acid, 7-amino-4-hydroxy-2-naphthalenesulfonic acid, and phenylphosphonic acid.

芳香族酸可以游離酸形式、以各別鹽形式(例如鹼金屬鹽或銨鹽)、以其水合物形式或以上文所提及者之任何適宜組合形式添加至活化組合物中。若適用，其亦可以酸酐形式添加(例如鄰苯二甲酸酐能夠在水性介質中形成鄰苯二甲酸)。 Aromatic acids can be added to the activating composition in free acid form, in the form of individual salts (e.g., alkali metal or ammonium salts), in the form of hydrates, or in any suitable combination of those mentioned above. If applicable, it can also be added in the form of acid anhydride (for example, phthalic anhydride is capable of forming phthalic acid in an aqueous medium).

本發明活化組合物中兩種或更多種芳香族酸之使用有利地使得較精細鈀粒子(亦稱為晶種)形成於如此處理之矽基材表面上。兩種或更多種芳香族酸之添加亦得到矽基材表面上如此沈積之鈀粒子之經改良均勻性。在僅具有一種芳香族酸或沒有任何芳香族酸下，鈀粒子極其粗糙且較不均勻地分佈於矽基材表面上(參見比較實例)。 The use of two or more aromatic acids in the activating composition of the present invention advantageously allows finer palladium particles (also known as seed crystals) to form on the surface of the silicon substrate thus treated. The addition of two or more aromatic acids also results in improved uniformity of the palladium particles so deposited on the surface of the silicon substrate. With or without one aromatic acid, the palladium particles are extremely rough and relatively unevenly distributed on the surface of the silicon substrate (see Comparative Example).

因此，活化組合物包含兩種或更多種芳香族酸。發明者已發現當在活化組合物中使用兩種或更多種芳香族酸時，矽基材之表面覆蓋 更均勻且個別粒子更小。 Therefore, the activating composition contains two or more aromatic acids. The inventors have discovered that when two or more aromatic acids are used in the activation composition, the surface of the silicon substrate is covered More uniform and smaller individual particles.

活化組合物中之芳香族酸之濃度(在此背景中此意指所用之所有芳香族酸之總濃度)在較佳0.1mg/L至1000mg/L、更佳1mg/L至750mg/L、甚至更佳10mg/L或40mg/L至500mg/L範圍內。在一些情形下在該等範圍之外之濃度使得獲得較少本發明之有益效應，例如使用鈀晶種處理之表面之均勻覆蓋。另外，可出現一些芳香族酸之溶解性問題。 The concentration of aromatic acids in the activating composition (which in this context means the total concentration of all aromatic acids used) is preferably 0.1 mg / L to 1000 mg / L, more preferably 1 mg / L to 750 mg / L, Even more preferably in the range of 10 mg / L or 40 mg / L to 500 mg / L. Concentrations outside these ranges in some cases allow less beneficial effects of the invention to be obtained, such as uniform coverage of surfaces treated with palladium seeds. In addition, there may be problems with the solubility of aromatic acids.

本發明活化組合物係水溶液。術語「水溶液」意指為溶液中之溶劑的優勢液體介質係水。可添加可與水混溶之其他液體，例如醇及可與水混溶之其他極性有機液體。較佳地，活化組合物僅包含水作為溶劑。 The activating composition of the present invention is an aqueous solution. The term "aqueous solution" means that the predominant liquid medium that is the solvent in the solution is water. Other water-miscible liquids can be added, such as alcohols and other polar organic liquids miscible with water. Preferably, the activating composition contains only water as a solvent.

本發明活化組合物包含鈀離子源。鈀離子源可係任何水溶性鈀鹽或鈀錯合物。較佳地，鈀離子源選自由以下組成之群：氯化鈀、硫酸鈀、硫酸錯合物形式之硫酸鈀、硝酸鈀及乙酸鈀，更佳選自由以下組成之群：氯化鈀、硫酸鈀、硝酸鈀及乙酸鈀。 The activating composition of the present invention comprises a source of palladium ions. The source of palladium ion can be any water-soluble palladium salt or palladium complex. Preferably, the palladium ion source is selected from the group consisting of palladium chloride, palladium sulfate, palladium sulfate in the form of a sulfuric acid complex, palladium nitrate, and palladium acetate, and more preferably selected from the group consisting of: palladium chloride, sulfuric acid Palladium, palladium nitrate and palladium acetate.

本發明活化組合物中之鈀離子之濃度較佳在0.001g/L至1g/L、更佳0.005g/L至0.5g/L、甚至更佳0.05g/L至0.25g/L範圍內。 The concentration of palladium ions in the activating composition of the present invention is preferably in the range of 0.001 g / L to 1 g / L, more preferably 0.005 g / L to 0.5 g / L, and even more preferably 0.05 g / L to 0.25 g / L.

本發明活化組合物進一步包含氟離子源。此氟離子源可係任何水溶性氟化物鹽或任何水溶性氟化物錯合物。較佳地，氟離子源選自氫氟酸、氟化銨及諸如氟化鉀、氟化鈉及氟化鋰等鹼金屬氟化物。 The activating composition of the present invention further comprises a fluoride ion source. This fluoride ion source can be any water-soluble fluoride salt or any water-soluble fluoride complex. Preferably, the fluoride ion source is selected from hydrofluoric acid, ammonium fluoride, and alkali metal fluorides such as potassium fluoride, sodium fluoride, and lithium fluoride.

存在於活化組合物中之氟離子之濃度較佳在0.075wt.%至4wt.%、更佳0.1wt.%至2wt.%、甚至更佳0.15wt.%至1wt.%範圍內。業內已知較高濃度之氟離子將導致來自欲使用本發明活化組合物處理之基材之矽原子的溶解增加。為處理極薄及易碎矽基材，因此在本發明活化組合物中使用較低濃度之氟離子係有利的。 The concentration of fluoride ions present in the activating composition is preferably in the range of 0.075 wt.% To 4 wt.%, More preferably 0.1 wt.% To 2 wt.%, Even more preferably 0.15 wt.% To 1 wt.%. It is known in the art that higher concentrations of fluoride ions will result in increased dissolution of silicon atoms from a substrate to be treated with the activating composition of the present invention. To handle extremely thin and fragile silicon substrates, it is advantageous to use a lower concentration of fluoride ions in the activating composition of the present invention.

本發明活化組合物較佳具有7或更低、更佳低於3、甚至更佳0至 2.5之pH。 The activating composition of the present invention preferably has 7 or less, more preferably less than 3, even more preferably 0 to PH of 2.5.

本發明活化組合物視情況包含選自由以下組成之群之甲烷磺酸及/或礦酸：硫酸、鹽酸、硝酸、磷酸、甲烷磺酸、氫溴酸、碘化氫、過氯酸、王水、次氯酸、碘酸及亞硝酸。較佳地，可選礦酸選自硫酸、鹽酸及硝酸。可選礦酸(或甲烷磺酸)之濃度在0.01wt.%至20wt.%或較佳0.1wt.%至10wt.%範圍內。 The activating composition of the present invention optionally includes a methanesulfonic acid and / or mineral acid selected from the group consisting of: sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, methanesulfonic acid, hydrobromic acid, hydrogen iodide, perchloric acid, aqua regia , Hypochlorous acid, iodic acid and nitrous acid. Preferably, the optional mineral acid is selected from sulfuric acid, hydrochloric acid and nitric acid. The concentration of the optional mineral acid (or methanesulfonic acid) is in the range of 0.01 wt.% To 20 wt.% Or preferably 0.1 wt.% To 10 wt.%.

本發明活化組合物視情況包含選自由以下組成之群之氧化劑：分子氧、諸如硝酸鉀等硝酸鹽源及過氧化氫。分子氧可以氣體進料形式添加至活化組合物中。業內已知氧化劑、甲烷磺酸及/或礦酸之可選添加可引起加速之活化製程。然而，並不總期望如此。 The activating composition of the present invention optionally includes an oxidant selected from the group consisting of molecular oxygen, a source of nitrate such as potassium nitrate, and hydrogen peroxide. Molecular oxygen can be added to the activation composition as a gas feed. It is known in the art that the optional addition of oxidants, methanesulfonic acids and / or mineral acids can cause accelerated activation processes. However, this is not always expected.

本發明活化組合物視情況包含選自由陽離子、非離子及陰離子表面活性劑組成之群之表面活性劑(業內亦稱為潤濕劑)。 The activating composition of the present invention optionally includes a surfactant (also known as a wetting agent in the industry) selected from the group consisting of cationic, nonionic and anionic surfactants.

本發明活化組合物可藉由將所有組份溶於水性液體介質(較佳水)中來製備。 The activating composition of the present invention can be prepared by dissolving all components in an aqueous liquid medium, preferably water.

本發明之用於活化至少一種矽基材之方法以給定順序包含以下步驟：(i)提供至少一種矽基材；(ii)使用本發明活化組合物活化該至少一種矽基材之表面之至少一部分。 The method for activating at least one silicon substrate of the present invention comprises the following steps in a given order: (i) providing at least one silicon substrate; (ii) activating the surface of the at least one silicon substrate using the activating composition of the present invention. At least a part.

欲用於本發明方法中之至少一種矽基材包含由諸如多晶矽(包括摻雜之多晶矽，例如p型摻雜之多晶矽及n型摻雜之多晶矽)及單晶矽等矽、氧化矽、氮化矽及氧氮化矽製得之表面。矽基材之整體可由上文所提及之材料或其組合中之任一者製得或其可僅包含由一或多種上文所提及之材料製得之表面。 At least one silicon substrate to be used in the method of the present invention includes silicon, silicon oxide, nitrogen, and the like, including polycrystalline silicon (including doped polycrystalline silicon, such as p-doped polycrystalline silicon and n-doped polycrystalline silicon) and single crystal silicon Surfaces made of silicon and silicon oxynitride. The entirety of the silicon substrate may be made of any of the materials or combinations thereof mentioned above or it may only include surfaces made of one or more of the materials mentioned above.

多晶矽之摻雜通常使用產生n型摻雜之多晶矽之供體(例如砷或磷)及產生p型摻雜之多晶矽之受體(例如硼或鋁)來進行。通常，該等 供體/受體以介於10-4-10-9wt.%之間之含量使用。若使用極高量之摻雜劑(通常介於10-3wt.%與10-4wt.%之間)，則獲得n及p型摻雜之多晶矽。在本發明之上下文中，n及p型摻雜之多晶矽亦理解為n及p型摻雜之多晶矽。可以如上文所述之類似方式摻雜氧化矽、氮化矽及氧氮化矽。 Doping of polycrystalline silicon is generally performed using a donor (such as arsenic or phosphorus) that generates n-doped polycrystalline silicon and an acceptor (such as boron or aluminum) that generates p-doped polycrystalline silicon. Generally, these donors / acceptors are used at a level between 10 -4 and -10 -9 wt.%. If extremely high amounts of dopants are used (typically between 10 -3 wt.% And 10 -4 wt.%), N- and p-type doped polycrystalline silicon is obtained. In the context of the present invention, n- and p-doped polycrystalline silicon is also understood as n- and p-doped polycrystalline silicon. Silicon oxide, silicon nitride, and silicon oxynitride can be doped in a similar manner as described above.

較佳地，在本發明方法中使用多晶矽、p型摻雜之多晶矽及n型摻雜之多晶矽；更佳使用p型摻雜之多晶矽。 Preferably, polycrystalline silicon, p-doped polycrystalline silicon and n-doped polycrystalline silicon are used in the method of the present invention; more preferably, p-doped polycrystalline silicon is used.

藉由業內已知方式使該至少一種矽基材之表面之至少一部分與本發明活化組合物接觸(在步驟(ii)中)且藉此該至少一種矽基材之表面經活化。在矽基材表面與活化組合物之間之此接觸方式尤其包括將矽基材浸沒於組合物中或擦拭、噴霧或以其他方式將活化組合物引至該表面上。 At least a portion of the surface of the at least one silicon substrate is contacted (in step (ii)) with the activation composition of the present invention by means known in the art and thereby the surface of the at least one silicon substrate is activated. This means of contact between the surface of the silicon substrate and the activating composition includes, among other things, immersing the silicon substrate in the composition or wiping, spraying, or otherwise introducing the activating composition onto the surface.

在矽基材與本發明活化組合物接觸之後，將於矽基材之表面上形成薄且均勻分散之鈀晶種層。此步驟在業內係稱為活化。因此，如此處理之基材稱為「經活化」。 After the silicon substrate contacts the activating composition of the present invention, a thin and uniformly dispersed palladium seed layer will be formed on the surface of the silicon substrate. This step is known in the industry as activation. Therefore, the substrate thus treated is called "activated".

將基材與活化組合物接觸1秒至30分鐘、較佳30秒至10分鐘、更佳40秒至5分鐘、最佳45秒至2分鐘。端視經活化基材之期望性質，可應用在上文所述範圍外之接觸持續時間。 The substrate is contacted with the activating composition for 1 second to 30 minutes, preferably 30 seconds to 10 minutes, more preferably 40 seconds to 5 minutes, and most preferably 45 seconds to 2 minutes. Depending on the desired properties of the activated substrate, it can be applied for contact durations outside the ranges described above.

當與矽基材接觸時，活化溶液較佳具有在10℃至90℃、更佳15℃至50℃範圍內之溫度。 When in contact with the silicon substrate, the activation solution preferably has a temperature in the range of 10 ° C to 90 ° C, more preferably 15 ° C to 50 ° C.

應理解，在本發明之上下文中，可使用於矽基底上包含許多摻雜區(例如源極及汲極，S/D)、絕緣層(例如摻雜及未摻雜之氧化矽)及傳導層(例如摻雜及未摻雜之多晶矽、金屬)之半導體基材。該方法亦可應用於用於製造太陽能電池之單晶或多晶矽。 It should be understood that in the context of the present invention, it can be used for silicon substrates including many doped regions (such as source and drain, S / D), insulating layers (such as doped and undoped silicon oxide), and conduction Layers (such as doped and undoped polycrystalline silicon, metal) semiconductor substrates. This method can also be applied to monocrystalline or polycrystalline silicon used for manufacturing solar cells.

本發明之用於活化矽基材之方法可在步驟(ii)之後包含另一步驟(iii)於經活化之矽基材上無電電鍍金屬或金屬合金。 The method for activating a silicon substrate of the present invention may include another step (iii) after step (ii) to electrolessly plate a metal or a metal alloy on the activated silicon substrate.

無電電鍍係在無外部電子供應幫助之情形下之連續金屬膜之受控自催化沈積。無電金屬電鍍浴之主要組份係金屬離子源、錯合劑、還原劑及作為可選成份之穩定劑、細晶劑及pH調節劑(酸、鹼、緩衝劑)。錯合劑(業內亦稱為螯合劑)係用於螯合欲沈積之金屬且防止金屬自溶液沈澱(即，作為氫氧化物及諸如此類)。螯合金屬使得金屬為將金屬離子轉化為其金屬形式之還原劑可用。金屬沈積之另一形式係浸鍍。浸鍍係在無外部供應電子之幫助且無化學還原劑之情形下之金屬之另一沈積。該機制依賴於來自下伏基材之金屬代替為存在於浸鍍溶液中之金屬離子。在本發明之上下文中，無電電鍍應主要理解為在化學還原劑(本文係指「還原劑」)之幫助下自催化沈積。 Electroless plating is the controlled autocatalytic deposition of a continuous metal film without the assistance of an external electronic supply. The main components of electroless metal electroplating bath are metal ion source, complexing agent, reducing agent and stabilizer, fine crystal agent and pH adjusting agent (acid, alkali, buffer) as optional ingredients. Complexing agents (also known as chelating agents in the industry) are used to sequester the metal to be deposited and prevent the metal from precipitating from the solution (ie, as a hydroxide and the like). Chelating metals makes metals useful as reducing agents that convert metal ions into their metal form. Another form of metal deposition is immersion plating. Dip plating is another deposition of metal without the help of externally supplied electrons and without chemical reducing agents. This mechanism relies on the replacement of metal from the underlying substrate by metal ions present in the immersion plating solution. In the context of the present invention, electroless plating should be understood primarily as autocatalytic deposition with the help of chemical reducing agents (herein referred to as "reducing agents").

為調節當使用此一無電電鍍浴時無電金屬電鍍浴及欲形成金屬或金屬合金沈積物之性質，故將添加劑添加至無電電鍍浴中以改良無電電鍍浴及所形成金屬或金屬合金沈積物二者之性質。通常，對於許多金屬及金屬合金，無電金屬電鍍浴均為業內已知。 In order to adjust the properties of the electroless metal plating bath and the metal or metal alloy deposits to be formed when using this electroless plating bath, additives are added to the electroless plating bath to improve the electroless plating bath and the formed metal or metal alloy deposits. The nature of the person. Generally, electroless metal plating baths are known in the industry for many metals and metal alloys.

在步驟(iii)中金屬或金屬合金係沈積於經活化之矽基材上。較佳在步驟(iii)中沈積之金屬或金屬合金選自銅、鈷、鎳、銅合金、鈷合金及鎳合金。本發明之更佳實施例為欲沈積之金屬係鎳或其合金，此乃因矽化鎳係晶片製造中矽化鉭或矽化鈦之適宜替代。本文中能夠沈積鎳或鎳合金之無電金屬電鍍浴係稱為無電鎳電鍍浴。 The metal or metal alloy is deposited on the activated silicon substrate in step (iii). Preferably, the metal or metal alloy deposited in step (iii) is selected from the group consisting of copper, cobalt, nickel, copper alloy, cobalt alloy, and nickel alloy. A more preferred embodiment of the present invention is the metallic nickel or its alloy to be deposited, which is a suitable replacement for tantalum silicide or titanium silicide in the manufacture of nickel silicide wafers. An electroless metal plating bath capable of depositing nickel or a nickel alloy is referred to herein as an electroless nickel plating bath.

無電鎳電鍍浴含有至少一種鎳離子源，其可係任何水溶性鎳鹽或其他水溶性鎳化合物。較佳鎳離子源選自包含氯化鎳、硫酸鎳、乙酸鎳、甲烷磺酸鎳及碳酸鎳之群。無電鎳電鍍浴中之鎳離子濃度較佳在0.1g/l至60g/l(0.0017mol/l至1.022mol/l)、更佳2g/l至50g/l(0.034mol/l至0.852mol/l)、甚至更佳4g/l至10g/l(0.068mol/l至0.170mol/l)範圍內。 The electroless nickel plating bath contains at least one source of nickel ions, which can be any water-soluble nickel salt or other water-soluble nickel compound. Preferred nickel ion sources are selected from the group consisting of nickel chloride, nickel sulfate, nickel acetate, nickel methanesulfonate, and nickel carbonate. The nickel ion concentration in the electroless nickel plating bath is preferably 0.1 g / l to 60 g / l (0.0017 mol / l to 1.022 mol / l), more preferably 2 g / l to 50 g / l (0.034 mol / l to 0.852 mol / l l), even more preferably in the range of 4 g / l to 10 g / l (0.068 mol / l to 0.170 mol / l).

無電鎳電鍍浴進一步含有選自以下之還原劑：次膦酸鹽化合 物，例如次膦酸鈉、次膦酸鉀及次膦酸銨；基於硼之還原劑，例如胺基硼烷(如二甲基胺基硼烷(DMAB))、鹼金屬硼氫化物(如NaBH4、KBH4)；甲醛；肼及其混合物。無電鎳電鍍浴中之還原劑濃度(在此處其意指還原劑之總量)通常在0.01mol/l至1.5mol/l範圍內。 The electroless nickel plating bath further contains a reducing agent selected from the group consisting of phosphinate compounds such as sodium phosphinate, potassium phosphinate, and ammonium phosphinate; boron-based reducing agents such as aminoborane (such as dimethyl Aminoamine borane (DMAB)), alkali metal borohydride (such as NaBH 4 , KBH 4 ); formaldehyde; hydrazine and mixtures thereof. The concentration of the reducing agent in the electroless nickel plating bath (which means the total amount of the reducing agent here) is usually in the range of 0.01 mol / l to 1.5 mol / l.

無電鎳電鍍浴之pH值較佳在3.5至8.5、更佳4至6之範圍內。因為電鍍溶液在其操作期間由於H3O+離子形成從而傾向於變得酸性更強，故可藉由添加浴溶性且浴相容之鹼性物質(例如鈉、鉀或銨之氫氧化物、碳酸鹽及碳酸氫鹽)來定期或連續調整pH。可藉由以最高30g/l、更佳2g/l至10g/l之量添加多種緩衝化合物(例如乙酸、丙酸、硼酸或諸如此類)來改良電鍍溶液之操作pH之穩定性。 The pH value of the electroless nickel plating bath is preferably in the range of 3.5 to 8.5, more preferably 4 to 6. Because the plating solution tends to become more acidic due to the formation of H 3 O + ions during its operation, it is possible to add bath-soluble and bath-compatible alkaline substances (such as sodium, potassium, or ammonium hydroxides, Carbonate and bicarbonate) to periodically or continuously adjust the pH. The stability of the operating pH of the plating solution can be improved by adding various buffer compounds (such as acetic acid, propionic acid, boric acid, or the like) in an amount of up to 30 g / l, more preferably 2 g / l to 10 g / l.

在本發明之一實施例中，選擇羧酸、多胺及磺酸或其混合物作為錯合劑。可用羧酸包括單-、二-、三-及四-羧酸。羧酸可經多種取代基部分(例如羥基或胺基)取代，且該等酸可以其鈉、鉀或銨鹽形式引入無電鎳電鍍浴中。一些錯合劑(例如乙酸)亦可用作緩衝劑，且此等添加組份之適當濃度可針對任一電鍍溶液鑒於該等組份之雙重功能來最佳化。 In one embodiment of the present invention, a carboxylic acid, a polyamine, a sulfonic acid, or a mixture thereof is selected as a complexing agent. Useful carboxylic acids include mono-, di-, tri- and tetra-carboxylic acids. The carboxylic acid can be substituted with a variety of substituent moieties, such as hydroxyl or amine groups, and the acids can be introduced into the electroless nickel plating bath in the form of their sodium, potassium or ammonium salts. Some complexing agents (such as acetic acid) can also be used as buffers, and the appropriate concentration of these added components can be optimized for any plating solution in view of the dual functions of these components.

此等用作錯合劑之羧酸之實例包括：如WO 2013/113810中所揭示之亞胺基琥珀酸、亞胺基二琥珀酸、其衍生物及其鹽；單羧酸，例如乙酸、羥基乙酸、胺基乙酸、2-胺基丙酸、2-羥基丙酸(乳酸)；二羧酸，例如琥珀酸、胺基琥珀酸、羥基琥珀酸、丙二酸、羥基丁二酸、酒石酸、蘋果酸；三羧酸，例如2-羥基-1,2,3-丙烷三甲酸；及四羧酸，例如乙二胺四乙酸(EDTA)。最佳錯合劑選自由單羧酸及二羧酸組成之群。在一實施例中，利用上述錯合劑中之兩者或更多者之混合物。存在於無電鎳電鍍浴中之錯合劑濃度或(在使用多於一種錯合劑之情形下)所有錯合劑一起之濃度較佳在0.01mol/l至2.5mol/l、更佳0.05mol/l至1.0mol/l之範圍內。 Examples of such carboxylic acids used as complexing agents include: iminosuccinic acid, iminodisuccinic acid, derivatives thereof, and salts thereof as disclosed in WO 2013/113810; monocarboxylic acids such as acetic acid, hydroxy Acetic acid, aminoacetic acid, 2-aminopropionic acid, 2-hydroxypropionic acid (lactic acid); dicarboxylic acids such as succinic acid, aminosuccinic acid, hydroxysuccinic acid, malonic acid, hydroxysuccinic acid, tartaric acid, Malic acid; tricarboxylic acids such as 2-hydroxy-1,2,3-propanetricarboxylic acid; and tetracarboxylic acids such as ethylenediaminetetraacetic acid (EDTA). The best complexing agent is selected from the group consisting of monocarboxylic acids and dicarboxylic acids. In one embodiment, a mixture of two or more of the above complexing agents is used. The concentration of the complexing agent present in the electroless nickel plating bath or (in the case of using more than one complexing agent) the concentration of all the complexing agents together is preferably from 0.01 mol / l to 2.5 mol / l, more preferably from 0.05 mol / l to Within 1.0 mol / l.

無電鎳電鍍浴視情況含有至少一種穩定劑。需要此穩定劑以提供足夠的浴壽命、合理的電鍍速率並控制如此沈積之鎳合金中之磷或硼含量。適宜可選穩定劑係(但不限於)重金屬離子，例如鎘、鉈、鉍、鉛及銻離子；含碘化合物，例如碘化物及碘酸鹽；含硫化合物，例如硫氰酸鹽、硫脲及巰基烷烴磺酸(如3-巰基丙烷磺酸)或如WO 2013/013941中所揭示之自其衍生之各別二硫化物；及不飽和有機酸，例如馬來酸及伊康酸(itaconic acid)；或如藉由EP 2 671 969 A1所教示之彼等之適宜經取代之炔烴。使用穩定劑之組合亦在本發明之範圍內，如藉由WO 2013/113810所教示，該等組合例如鉍離子與巰基苯甲酸、巰基羧酸及/或巰基磺酸。無電鎳電鍍浴可包含電鍍速率調節劑(例如揭示於歐洲專利申請案EP 14198380.9中之彼等)以有利地降低電鍍速率並使電鍍浴穩定。無電鎳電鍍浴中之至少一種可選穩定劑之濃度在0.1mg/l至100mg/l、較佳0.5mg/l至30mg/l範圍內。 The electroless nickel plating bath optionally contains at least one stabilizer. This stabilizer is needed to provide sufficient bath life, a reasonable plating rate, and control the phosphorus or boron content in the nickel alloy so deposited. Suitable optional stabilizers are (but not limited to) heavy metal ions, such as cadmium, scandium, bismuth, lead, and antimony ions; iodine-containing compounds, such as iodides and iodates; sulfur-containing compounds, such as thiocyanates, thioureas And mercaptoalkanesulfonic acids (such as 3-mercaptopropanesulfonic acid) or individual disulfides derived therefrom as disclosed in WO 2013/013941; and unsaturated organic acids such as maleic acid and itaconic acid (itaconic acid); or their suitable substituted alkynes as taught by EP 2 671 969 A1. It is also within the scope of the invention to use combinations of stabilizers, such as taught by WO 2013/113810, such combinations as bismuth ion and mercaptobenzoic acid, mercaptocarboxylic acid and / or mercaptosulfonic acid. Electroless nickel plating baths may contain plating rate modifiers (such as those disclosed in European patent application EP 14198380.9) to advantageously reduce the plating rate and stabilize the plating bath. The concentration of at least one optional stabilizer in the electroless nickel plating bath is in the range of 0.1 mg / l to 100 mg / l, preferably 0.5 mg / l to 30 mg / l.

無電鎳電鍍浴可包含(但不必需包含)其他調節劑，例如潤濕劑、表面活性劑、加速劑、增亮劑、晶粒細化添加劑等。該等組份為業內所已知。 The electroless nickel plating bath may contain (but not necessarily include) other modifiers, such as wetting agents, surfactants, accelerators, brighteners, grain refinement additives, and the like. These components are known in the industry.

在次膦酸鹽化合物用作鎳之還原劑之情形下，獲得含有鎳及磷之合金沈積物。該合金沈積物中之磷之量尤其取決於無電鎳電鍍浴中之次膦酸鹽及鎳離子及可選穩定劑之濃度。較佳地，該合金沈積物中之磷之量在5wt.%至15wt.%範圍內，餘量為鎳。 In the case where a phosphinate compound is used as a reducing agent for nickel, an alloy deposit containing nickel and phosphorus is obtained. The amount of phosphorus in the alloy deposit depends in particular on the concentration of the phosphinate and nickel ions and optional stabilizers in the electroless nickel plating bath. Preferably, the amount of phosphorus in the alloy deposit is in the range of 5 wt.% To 15 wt.%, And the balance is nickel.

在基於硼之還原劑用作鎳之還原劑之情形下，獲得含有鎳及硼之合金沈積物。該合金沈積物中硼之量尤其取決於無電鎳電鍍浴中之基於硼之還原劑及鎳離子及可選穩定劑之濃度或pH值。較佳地，該合金沈積物中硼之量在1wt.%至10wt.%範圍內，餘量為鎳。 In the case where a boron-based reducing agent is used as a reducing agent for nickel, an alloy deposit containing nickel and boron is obtained. The amount of boron in the alloy deposit depends in particular on the concentration or pH of the boron-based reducing agent and nickel ions and optional stabilizers in the electroless nickel plating bath. Preferably, the amount of boron in the alloy deposit is in the range of 1 wt.% To 10 wt.%, And the balance is nickel.

在肼及甲醛中之一或多者用作鎳之還原劑之情形下，獲得純鎳沈積物。 Where one or more of hydrazine and formaldehyde are used as a reducing agent for nickel, a pure nickel deposit is obtained.

無電鎳電鍍浴可視情況包含第二金屬離子源，例如鉬、錸或鎢離子。該等第二金屬離子可較佳以水溶性鹽或諸如MoO2(OH)2、ReO2(OH)2、WO2(OH)2、Na2MoO4、Na2ReO4及Na2WO4等化合物及其各別水合物形式來添加。 The electroless nickel plating bath optionally contains a second metal ion source, such as molybdenum, rhenium, or tungsten ions. The second metal ions may preferably be water-soluble salts or such as MoO 2 (OH) 2 , ReO 2 (OH) 2 , WO 2 (OH) 2 , Na 2 MoO 4 , Na 2 ReO 4 and Na 2 WO 4 And other compounds and their respective hydrate forms.

添加至無電鎳電鍍浴中之第二金屬離子之量較佳在0.01mol/l至0.2mol/l、更佳0.05mol/l至0.15mol/l範圍內。無電鎳電鍍浴中之第二金屬離子之量可足以達到經沈積鎳合金中第二金屬之4wt.%至20wt.%之濃度。 The amount of the second metal ion added to the electroless nickel plating bath is preferably in the range of 0.01 mol / l to 0.2 mol / l, more preferably 0.05 mol / l to 0.15 mol / l. The amount of the second metal ion in the electroless nickel plating bath may be sufficient to reach a concentration of 4 wt.% To 20 wt.% Of the second metal in the deposited nickel alloy.

或者，在步驟(iii)中，銅或銅合金可以金屬或金屬合金形式沈積於經活化之矽基材上。在太陽能電池之製造中，銅或其合金通常沈積於矽基材上。無電銅或銅合金浴包含銅離子源、還原劑、錯合劑及通常穩定劑。US 7,220,296；WO 2014/154702；G.O.Mallory，J.B.Hajdu，Electroless Plating：Fundamentals And Applications，重印版，American Electroplaters and Surface Finishers Society，第289-295頁；US 4,617,205；US 2008/0223253及具體而言歐洲專利申請案EP 14198380.9係以引用方式全部併入本文中並闡述無電銅或銅合金沈積中所用之該等上文所提及之化合物及其他適宜添加劑(以可適用的濃度及可用的參數)。 Alternatively, in step (iii), the copper or copper alloy may be deposited on the activated silicon substrate in the form of a metal or metal alloy. In the manufacture of solar cells, copper or its alloys are usually deposited on a silicon substrate. An electroless copper or copper alloy bath contains a source of copper ions, a reducing agent, a complexing agent, and a general stabilizer. US 7,220,296; WO 2014/154702; GOMallory, JBHajdu, Electroless Plating: Fundamentals And Applications, Reprint, American Electroplaters and Surface Finishers Society, pages 289-295; US 4,617,205; US 2008/0223253 and specifically European patents Application EP 14198380.9 is incorporated herein by reference in its entirety and describes the above-mentioned compounds and other suitable additives (with applicable concentrations and parameters available) used in the electroless copper or copper alloy deposition.

鈷及其合金可用作矽基材上之障壁層。此等障壁層用於晶片製造中。其置於(例如)銅線與矽層之間且欲抑制銅至矽層之遷移。具體而言，三元鈷-鎢-磷及鈷-鉬-磷合金可用於此目的。無電鈷或鈷合金浴包含銅離子源、還原劑、錯合劑及通常穩定劑。US 2005/0161338、WO 2013/135396及歐洲專利申請案EP 14198380.9闡述用於無電鈷或鈷合金沈積中之該等上文所提及之化合物及其他適宜添加劑(以可適用的濃度及可用參量)且以引用方式全部併入本文中。 Cobalt and its alloys can be used as a barrier layer on a silicon substrate. These barrier layers are used in wafer manufacturing. It is placed, for example, between a copper wire and a silicon layer and is intended to inhibit copper-to-silicon layer migration. Specifically, ternary cobalt-tungsten-phosphorus and cobalt-molybdenum-phosphorus alloys can be used for this purpose. An electroless cobalt or cobalt alloy bath contains a source of copper ions, a reducing agent, a complexing agent, and a usual stabilizer. US 2005/0161338, WO 2013/135396 and European patent application EP 14198380.9 describe these compounds and other suitable additives (in applicable concentrations and parameters available) for use in the electroless cobalt or cobalt alloy deposition And incorporated herein by reference in its entirety.

所沈積之金屬或金屬合金層較佳具有低於150nm之厚度，其更 佳在1nm至50nm範圍內，其甚至更佳在2nm至20nm範圍內。 The deposited metal or metal alloy layer preferably has a thickness of less than 150 nm, which is more It is preferably in the range of 1 nm to 50 nm, and it is even more preferably in the range of 2 nm to 20 nm.

至少一種矽基材或至少一部分之其表面可藉助噴霧、擦拭、浸泡、浸沒或藉由其他適宜方式來與無電金屬電鍍浴及活化組合物接觸。本發明製程中之步驟(iii)之無電金屬電鍍可以水平、捲到捲、垂直、垂直輸送或噴鍍設備來實施。可用於實施本發明製程之尤其適宜電鍍工具揭示於US 2012/0213914 A1中。 The surface of at least one silicon substrate or at least a portion thereof may be contacted with the electroless metal plating bath and the activation composition by spraying, wiping, dipping, immersing, or by other suitable means. The electroless metal plating of step (iii) in the process of the present invention can be performed by horizontal, roll-to-roll, vertical, vertical transport or spray coating equipment. A particularly suitable electroplating tool that can be used to implement the process of the present invention is disclosed in US 2012/0213914 A1.

矽基材可與無電金屬電鍍浴接觸1秒至30min、較佳30秒至10分鐘、更佳40秒至3分鐘、最佳45秒至3分鐘。矽基材與活化組合物及經活化之矽基材與無電金屬或金屬合金電鍍浴之接觸時間影響所獲得金屬或金屬合金層厚度。因此，熟習此項技術者可確定兩個步驟中達成某一金屬或金屬合金層厚度所需之接觸持續時間。 The silicon substrate can be contacted with the electroless metal plating bath for 1 second to 30 minutes, preferably 30 seconds to 10 minutes, more preferably 40 seconds to 3 minutes, and most preferably 45 seconds to 3 minutes. The contact time between the silicon substrate and the activating composition and the activated silicon substrate and the electroless metal or metal alloy plating bath affects the thickness of the obtained metal or metal alloy layer. Therefore, those skilled in the art can determine the contact duration required to achieve a certain metal or metal alloy layer thickness in two steps.

本發明之用於活化矽基材之方法可在步驟(iii)之後包含另一步驟(iv)熱處理矽基材且從而形成金屬矽化物。 The method for activating a silicon substrate of the present invention may include another step (iv) after step (iii) to heat treat the silicon substrate and thereby form a metal silicide.

至少一種矽基材可在介於300℃與750℃之間之溫度下在諸如氮或氬等惰性氣體中熱處理30秒至60秒。在熱處理表面上沈積有金屬或金屬合金層之矽基材之後，金屬擴散至矽基材中且形成金屬矽化物。此熱處理已在業內充分確立且有時稱為快速熱退火(通常縮寫為RTA)。US 6,406,743 B1教示可用於本發明之上下文中之各種熱處理方案。 At least one silicon substrate can be heat treated in an inert gas such as nitrogen or argon at a temperature between 300 ° C and 750 ° C for 30 seconds to 60 seconds. After the silicon substrate having the metal or metal alloy layer deposited on the heat-treated surface, the metal diffuses into the silicon substrate and forms a metal silicide. This heat treatment is well established in the industry and is sometimes referred to as rapid thermal annealing (commonly abbreviated as RTA). US 6,406,743 B1 teaches various heat treatment schemes that can be used in the context of the present invention.

在熱處理之後之任何留在矽基材表面上之剩餘金屬或金屬合金可藉由濕化學蝕刻、化學機械平坦化(或任何其他適宜方式)來移除，從而在矽基材表面上留下金屬矽化物。移除金屬或金屬合金之方式為業內已知。鎳或合其金可藉由兩步蝕刻來移除，如US 6,406,743 B1中所揭示。 Any remaining metal or metal alloy remaining on the surface of the silicon substrate after heat treatment can be removed by wet chemical etching, chemical mechanical planarization (or any other suitable method), thereby leaving metal on the surface of the silicon substrate Silicide. Methods for removing metals or metal alloys are known in the art. Nickel or alloys can be removed by two-step etching, as disclosed in US 6,406,743 B1.

本發明方法可包含進一步沖洗、清洗、蝕刻及預處理步驟，其 皆為業內所已知。 The method of the present invention may include further rinsing, cleaning, etching and pretreatment steps, which Both are known in the industry.

本發明方法具體而言適宜形成由金屬矽化物製得之互連，例如矽化鎳互連。該等互連可例示性用於MOS電晶體、CMOS電晶體、IC基材(VLSI)之製造中。含有此等互連之產品可係記憶條(USB條)、MS卡、SD卡、功率二極體及功率電晶體。或者，本發明方法可用於在矽基材上形成障壁層，例如鈷合金障壁層。其亦可用於矽基材之金屬化中以用於生產太陽能電池。 The method of the present invention is particularly suitable for forming interconnects made of metal silicides, such as nickel silicide interconnects. These interconnections can be exemplarily used in the manufacture of MOS transistors, CMOS transistors, and IC substrates (VLSI). Products containing these interconnections can be memory sticks (USB sticks), MS cards, SD cards, power diodes and power transistors. Alternatively, the method of the present invention can be used to form a barrier layer, such as a cobalt alloy barrier layer, on a silicon substrate. It can also be used in the metallization of silicon substrates for the production of solar cells.

本發明之優點係可獲得具有小於10nm或甚至小於5nm之層厚度之極薄且均勻分佈之鈀晶種層。然後，該等鈀晶種層使得50nm或25nm或甚至15nm或更薄之超薄金屬或金屬合金層(例如鎳或鎳合金層)沈積於其上。由於極薄且均勻分佈之鈀晶種層，形成於其上之金屬或金屬合金層較為平整、平坦且光滑(其可分別藉由例如原子力顯微術及XRF來量測；參見實例5)。然後，如此形成之金屬或金屬合金層可不需要或僅需要減少之化學機械平坦化步驟而轉化為金屬矽化物。 An advantage of the present invention is that an extremely thin and uniformly distributed palladium seed layer having a layer thickness of less than 10 nm or even less than 5 nm can be obtained. The palladium seed layers then deposit an ultra-thin metal or metal alloy layer (such as a nickel or nickel alloy layer) at 50 nm or 25 nm or even 15 nm or less. Due to the extremely thin and uniformly distributed palladium seed layer, the metal or metal alloy layer formed thereon is relatively flat, flat and smooth (which can be measured by, for example, atomic force microscopy and XRF; see Example 5). The metal or metal alloy layer thus formed may then be converted to a metal silicide without or only requiring a reduced chemical mechanical planarization step.

現將藉由參照以下非限制性實例來對本發明加以說明。 The invention will now be illustrated by reference to the following non-limiting examples.

實例Examples

藉由SEM(Zeiss Ultra Plus，SE2檢測器，加速電壓3.0kV或5.0kV，數據在個別圖中給出)目測分析基材。使用來自Olympus之Stream軟體來測定表面覆蓋率以量化所量測之SEM圖片。 The substrate was visually analyzed by SEM (Zeiss Ultra Plus, SE2 detector, acceleration voltage 3.0 kV or 5.0 kV, data given in separate figures). Stream software from Olympus was used to determine surface coverage to quantify the measured SEM images.

在各基材之5個點處藉由XRF使用XRF儀器Fischerscope XDV-SDD(Helmut Fischer GmbH,Germany)來量測金屬(合金)沈積厚度。藉由假設沈積物之層狀結構，可自此XRF數據計算出層厚度。 The metal (alloy) deposition thickness was measured at 5 points on each substrate by XRF using an XRF instrument Fischerscope XDV-SDD (Helmut Fischer GmbH, Germany). By assuming the layered structure of the sediment, the layer thickness can be calculated from this XRF data.

藉由掃描原子力顯微鏡(Digital Instruments,NanoScope，配備有來自Nanosensors之具有小於7nm之尖部半徑之PointProbe®)來測定表面之光滑度(或粗糙度)，掃描大小：5倍2×2μm，以輕敲模式掃描。藉由該等量測獲得平均粗糙度(SA)、最大高度差(ST)及RSAI值(相對表 面積增加)且利用以下各別實例提供。 The surface smoothness (or roughness) was measured by a scanning atomic force microscope (Digital Instruments, NanoScope, equipped with PointProbe ® with a tip radius of less than 7 nm from Nanosensors), scan size: 5 times 2 × 2 μm, light Tap mode scan. The average roughness (S A ), the maximum height difference (S T ), and the RSAI value (increased relative surface area) were obtained by these measurements and provided using the following respective examples.

實例1(比較)：Example 1 (comparative):

在室溫下將n型摻雜之多晶矽基材浸沒於含有0.1g/l Pd2+離子(來自PdSO4)及1wt.% HF之水溶液中持續120秒。表面由鈀粒子不均勻覆蓋，其中平均表面覆蓋率為(32.0±1.3)%(參見圖1)。 An n-type doped polycrystalline silicon substrate was immersed in an aqueous solution containing 0.1 g / l Pd 2+ ions (from PdSO 4 ) and 1 wt.% HF at room temperature for 120 seconds. The surface is covered unevenly by palladium particles, where the average surface coverage is (32.0 ± 1.3)% (see Figure 1).

實例2(比較)：Example 2 (comparison):

在室溫下將n型摻雜之多晶矽基材浸沒於含有0.1g/l Pd2+離子(來自PdSO4)、1wt.% HF及0.5ml/l冰乙酸之水溶液中持續120秒。表面由鈀粒子不均勻覆蓋，其中平均表面覆蓋率為(32.0±1.2)%(參見圖2)。 An n-type doped polycrystalline silicon substrate was immersed in an aqueous solution containing 0.1 g / l Pd 2+ ions (from PdSO 4 ), 1 wt.% HF, and 0.5 ml / l glacial acetic acid at room temperature for 120 seconds. The surface is covered unevenly by palladium particles, where the average surface coverage is (32.0 ± 1.2)% (see Figure 2).

實例3(比較)：Example 3 (comparative):

在室溫下將n型摻雜之多晶矽基材浸沒於0.1g/l Pd2+離子(來自PdSO4)，1wt.% HF之水溶液(其進一步包含如表I中所給出之芳香族酸)中持續120秒。結果及處理條件亦於該表中給出。 An n-type doped polycrystalline silicon substrate was immersed in an aqueous solution of 0.1 g / l Pd 2+ ions (from PdSO 4 ), 1 wt.% HF at room temperature (which further contained an aromatic acid as given in Table I ) For 120 seconds. The results and processing conditions are also given in the table.

1比較實例；2本發明實例 1 Comparative Example; 2 Example of the invention

與不含有芳香族酸之比較實例1及2相比，比較實例a.、c.及d.均顯示顯著改良之含有鈀之矽表面之表面覆蓋。然而，使用對甲苯磺酸之比較實例b.甚至導致比彼等實例更差的表面覆蓋。與其相比，當在本發明實例e.中使用多於一種芳香族酸時，表面覆蓋優良至幾乎完全覆蓋。應考慮到在此情形下浸沒時間比在許多比較實例中更短且總濃度與在大多比較實例中相同。因此，兩種或更多種芳香族酸之組合協同促進製程且使得獲得經改良之表面覆蓋。 Compared to Comparative Examples 1 and 2 which did not contain aromatic acids, Comparative Examples a., C., And d. All showed significantly improved surface coverage of the palladium-containing silicon surface. However, comparative example b. Using p-toluenesulfonic acid resulted in even worse surface coverage than their examples. In contrast, when more than one aromatic acid is used in Example e. Of the present invention, the surface coverage is excellent to almost completely. It should be taken into account that in this case the immersion time is shorter than in many comparative examples and the total concentration is the same as in most comparative examples. Therefore, the combination of two or more aromatic acids synergistically facilitates the process and allows for improved surface coverage.

實例4：Example 4:

將多晶矽基材浸沒於各自含有0.1g/l Pd2+離子(來自PdSO4)、1wt.% HF及如下表II中可見之各別濃度之一或多種芳香族酸之水溶液中持續60秒或120秒。 The polycrystalline silicon substrate is immersed in an aqueous solution each containing 0.1 g / l Pd 2+ ions (from PdSO 4 ), 1 wt.% HF, and one or more aromatic acids at various concentrations as seen in Table II below for 60 seconds or 120 seconds.

1比較實例；2本發明實例 1 Comparative Example; 2 Example of the invention

與比較實例1及2相比，表1之活化溶液均改良了基材表面之覆蓋。如SEM圖片中所見之個別粒子大多較小且相當均勻地分散於基材之整個表面上。可看到在活化組合物中兩種或更多種芳香族酸之使用 引起表面上之甚至更顯著均勻覆蓋及粒子分佈(表1中之條目d.及e.)。亦可看到，當與比較實例4a.至4c.相比時，自本發明實例4d.及4e.所獲得之個別粒子較小且實質上在表面上未形成較大聚集粒子。 Compared with Comparative Examples 1 and 2, the activation solution of Table 1 improved the coverage of the substrate surface. The individual particles, as seen in the SEM picture, are mostly small and fairly uniformly dispersed over the entire surface of the substrate. The use of two or more aromatic acids can be seen in the activating composition Causes even more significant uniform coverage and particle distribution on the surface (entries d. And e. In Table 1). It can also be seen that when compared with Comparative Examples 4a. To 4c., The individual particles obtained from Examples 4d. And 4e. Of the present invention are smaller and substantially do not form larger aggregate particles on the surface.

因此，發現協同效應起因於活化溶液中兩種或更多種芳香族酸之使用。 Therefore, it was found that the synergistic effect results from the use of two or more aromatic acids in the activation solution.

實例5(本發明)：Example 5 (present invention):

將n型摻雜之多晶矽基材浸沒於實例3e之水性活化組合物中分別持續60秒(實例5a)及120秒(實例5b)。在65℃下將如此活化之矽基材浸沒至各自具有4.3之pH且含有6g/l鎳離子(以硫酸鎳形式提供)、二羧酸、三羧酸及羥基羧酸作為錯合劑以及0.25g/l二甲基胺基硼烷作為還原劑之無電鎳電鍍浴中持續600秒。 The n-type doped polycrystalline silicon substrate was immersed in the aqueous activated composition of Example 3e for 60 seconds (Example 5a) and 120 seconds (Example 5b). The thus-activated silicon substrate was immersed at 65 ° C to each have a pH of 4.3 and contained 6 g / l of nickel ions (provided as nickel sulfate), dicarboxylic acid, tricarboxylic acid, and hydroxycarboxylic acid as complexing agents and 0.25 g / l dimethylaminoborane as a reducing agent in an electroless nickel plating bath for 600 seconds.

矽基材經鎳硼合金均勻覆蓋。厚度及粗糙度可參見表III。 The silicon substrate is uniformly covered by a nickel boron alloy. See Table III for thickness and roughness.

藉由本發明處理獲得鈀及鎳硼二者之極薄層。該等層亦極光滑且顯示極小粗糙度偏差，此在當製造目前的半導體裝置時係非常合意的。實例5a之AFM圖片顯示於圖8中。 An extremely thin layer of both palladium and nickel boron is obtained by the treatment of the invention. These layers are also extremely smooth and show minimal roughness deviations, which is very desirable when manufacturing current semiconductor devices. The AFM picture of Example 5a is shown in Figure 8.

Claims (14)

一種用於活化矽基材之活化組合物，其中該活化組合物係包含鈀離子源及氟離子源之水溶液，其特徵在於其包含至少兩種選自由以下組成之群之芳香族酸：芳香族羧酸、芳香族磺酸、芳香族亞磺酸、芳香族膦酸及芳香族次膦酸，其中該活化組合物中之該至少兩種芳香族酸之總濃度在0.1mg/L至1000mg/L範圍內。An activation composition for activating a silicon substrate, wherein the activation composition is an aqueous solution containing a source of palladium ions and a source of fluoride ions, characterized in that it contains at least two aromatic acids selected from the group consisting of: aromatic Carboxylic acid, aromatic sulfonic acid, aromatic sulfinic acid, aromatic phosphonic acid and aromatic phosphinic acid, wherein the total concentration of the at least two aromatic acids in the activated composition is 0.1 mg/L to 1000 mg/ Within the range of L. 如請求項1之活化組合物，其中該至少兩種芳香族酸選自由以下組成之群：芳香族羧酸、芳香族磺酸及芳香族膦酸。The activation composition of claim 1, wherein the at least two aromatic acids are selected from the group consisting of aromatic carboxylic acids, aromatic sulfonic acids, and aromatic phosphonic acids. 如請求項1或2之活化組合物，其中該至少兩種芳香族酸選自式(I)至(II)之芳香族酸
Figure TWI680206B_C0001
Figure TWI680206B_C0002
其中R1至R14彼此獨立選自由以下組成之群：氫、烷基、芳基、鹵化物、胺基、磺酸部分、羧酸部分、膦酸部分、硝基及羥基，前提係R1至R14中之至少一者係磺酸部分、羧酸部分或膦酸部分。The activation composition according to claim 1 or 2, wherein the at least two aromatic acids are selected from aromatic acids of formula (I) to (II)
Figure TWI680206B_C0001
Figure TWI680206B_C0002
Wherein R 1 to R 14 are independently selected from the group consisting of hydrogen, alkyl, aryl, halide, amine, sulfonic acid moiety, carboxylic acid moiety, phosphonic acid moiety, nitro and hydroxyl, provided that R 1 At least one of R 14 is a sulfonic acid moiety, a carboxylic acid moiety, or a phosphonic acid moiety. 如請求項3之活化組合物，其中該至少兩種芳香族酸中之一者包含磺酸部分。The activation composition according to claim 3, wherein one of the at least two aromatic acids includes a sulfonic acid moiety. 如請求項3之活化組合物，其中該至少兩種芳香族酸中之一者包含羧酸部分。The activation composition according to claim 3, wherein one of the at least two aromatic acids includes a carboxylic acid moiety. 如請求項3之活化組合物，其中該至少兩種芳香族酸中之一者包含磺酸部分且該至少兩種芳香族酸中之另一者包含羧酸部分。The activation composition of claim 3, wherein one of the at least two aromatic acids includes a sulfonic acid moiety and the other of the at least two aromatic acids includes a carboxylic acid moiety. 如請求項1或2中任一項之活化組合物，其中該至少兩種芳香族酸選自由以下組成之群：苯甲酸、1,2-苯二甲酸(鄰苯二甲酸)、1,3-苯二甲酸(間苯二甲酸)、1,4-苯二甲酸(對苯二甲酸)、1,2,3-苯三甲酸(半蜜臘酸)、1,2,4-苯三甲酸(偏苯三酸)、1,3,5-苯三甲酸(苯均三酸)、1,2,4,5-苯四甲酸(焦蜜石酸)、1,2,3,4,5-苯五甲酸、1,2,3,4,5,6-苯六甲酸(蜜臘酸)、2-硝基苯甲酸、3-硝基苯甲酸、4-硝基苯甲酸、2,5-二硝基苯甲酸、2,6-二硝基苯甲酸、3,5-二硝基苯甲酸、2,4-二硝基苯甲酸、3,4-二硝基苯甲酸、2-胺基苯甲酸、3-胺基苯甲酸、4-胺基苯甲酸、3,4-二胺基苯甲酸、3,5-二胺基苯甲酸、2,3-二胺基苯甲酸、2,4-二胺基苯甲酸、柳酸、對甲苯磺酸、1-萘甲酸、2-萘甲酸、2,6-萘二甲酸、2-萘磺酸、5-胺基-1-萘磺酸、5-胺基-2-萘磺酸、7-胺基-4-羥基-2-萘磺酸及苯基膦酸。The activation composition according to any one of claims 1 or 2, wherein the at least two aromatic acids are selected from the group consisting of benzoic acid, 1,2-phthalic acid (phthalic acid), 1,3 -Phthalic acid (isophthalic acid), 1,4-phthalic acid (terephthalic acid), 1,2,3-benzenetricarboxylic acid (hemimelic acid), 1,2,4-benzenetricarboxylic acid (Trimellitic acid), 1,3,5-benzenetricarboxylic acid (trimellitic acid), 1,2,4,5-benzenetetracarboxylic acid (pyromellitic acid), 1,2,3,4,5 -Mellitic acid, 1,2,3,4,5,6-mellitic acid (melanic acid), 2-nitrobenzoic acid, 3-nitrobenzoic acid, 4-nitrobenzoic acid, 2,5 -Dinitrobenzoic acid, 2,6-dinitrobenzoic acid, 3,5-dinitrobenzoic acid, 2,4-dinitrobenzoic acid, 3,4-dinitrobenzoic acid, 2-amine Benzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 3,4-diaminobenzoic acid, 3,5-diaminobenzoic acid, 2,3-diaminobenzoic acid, 2, 4-Diaminobenzoic acid, salicylic acid, p-toluenesulfonic acid, 1-naphthoic acid, 2-naphthoic acid, 2,6-naphthalenedicarboxylic acid, 2-naphthalenesulfonic acid, 5-amino-1-naphthalenesulfonic acid , 5-amino-2-naphthalenesulfonic acid, 7-amino-4-hydroxy-2-naphthalenesulfonic acid and phenylphosphonic acid. 如請求項1或2之活化組合物，其中該活化組合物中之該至少兩種芳香族酸之總濃度在1mg/L至750mg/L範圍內。The activation composition according to claim 1 or 2, wherein the total concentration of the at least two aromatic acids in the activation composition is in the range of 1 mg/L to 750 mg/L. 如請求項1或2之活化組合物，其中該活化組合物包含選自由以下組成之群之甲烷磺酸及/或礦酸：硫酸、鹽酸、硝酸、磷酸、甲烷磺酸、氫溴酸、碘化氫、過氯酸、王水(aqua regia)、次氯酸、碘酸及亞硝酸。The activation composition according to claim 1 or 2, wherein the activation composition comprises methanesulfonic acid and/or mineral acid selected from the group consisting of sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, methanesulfonic acid, hydrobromic acid, iodine Hydrogen chloride, perchloric acid, aqua regia, hypochlorous acid, iodic acid and nitrous acid. 一種用於活化至少一種矽基材之方法，其以給定順序包含以下步驟(i)提供該至少一種矽基材；(ii)使用如請求項1至9中任一項之活化組合物活化該至少一種矽基材之表面之至少一部分。A method for activating at least one silicon substrate comprising the following steps in a given order: (i) providing the at least one silicon substrate; (ii) activating using the activation composition according to any one of claims 1 to 9 At least a portion of the surface of the at least one silicon substrate. 如請求項10之方法，其中該等矽基材包含由以下製得之表面：氧化矽、多晶矽、p型摻雜之多晶矽、n型摻雜之多晶矽、氮化矽及氧氮化矽。The method of claim 10, wherein the silicon substrates include surfaces made of silicon oxide, polycrystalline silicon, p-type doped polycrystalline silicon, n-type doped polycrystalline silicon, silicon nitride, and silicon oxynitride. 如請求項10或11中任一項之方法，其中該方法在步驟(ii)後包含另一步驟(iii)在該經活化之矽基材上無電電鍍金屬或金屬合金。The method according to any one of claims 10 or 11, wherein the method after step (ii) includes another step (iii) electroless plating of a metal or metal alloy on the activated silicon substrate. 如請求項12之方法，其中該欲沈積之金屬選自銅、鈷、鎳、銅合金、鈷合金及鎳合金。The method of claim 12, wherein the metal to be deposited is selected from copper, cobalt, nickel, copper alloy, cobalt alloy, and nickel alloy. 如請求項12之方法，其中該方法在步驟(iii)後進一步包含(iv)熱處理該矽基材並從而形成金屬矽化物。The method of claim 12, wherein the method further comprises (iv) heat treating the silicon substrate after step (iii) and thereby forming a metal silicide.
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